CN104051745A - Simultaneous coating of fuel cell components - Google Patents

Simultaneous coating of fuel cell components Download PDF

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Publication number
CN104051745A
CN104051745A CN201410094397.5A CN201410094397A CN104051745A CN 104051745 A CN104051745 A CN 104051745A CN 201410094397 A CN201410094397 A CN 201410094397A CN 104051745 A CN104051745 A CN 104051745A
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Prior art keywords
solution
porous layer
base material
coated
coating
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CN201410094397.5A
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CN104051745B (en
Inventor
S.C.穆斯
B.M.霍塔林
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GM Global Technology Operations LLC
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GM Global Technology Operations LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8828—Coating with slurry or ink
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

Disclosed are methods for simultaneous application of multiple fuel cell component coatings onto a substrate. The method comprises providing a substrate, and simultaneously coating two or more solutions onto the substrate under laminar flow.

Description

In the time of fuel cell component, apply
Technical field
The embodiment of describing herein relates generally to the method for coating fuel cell components, and more specifically, and it relates to a plurality of fuel cell component coatings are applied to the method on base material simultaneously.
Background technology
Electrochemical conversion cells, is commonly referred to as fuel cell, by processing reaction thing, for example, by oxidation and the reduction of hydrogen and oxygen, produces electric energy.In some fuel cell systems, hydrogen or hydrogen-rich gas are used as reactant and by stream, are provided to the anode-side of fuel cell, and oxygen (as the form with aerial oxygen) is used as reactant, are provided to the cathode side of fuel cell by separated stream.Described anode and negative electrode promote described reactant electrochemical conversion to become electronics and positively charged ion (for hydrogen) and electronegative ion (for oxygen).Dielectric substrate makes anode separated with negative electrode to provide the selectivity of ion from anode to negative electrode to pass through, and forbids passing through of the electronics that produces simultaneously.The electronics producing be forced to flow through external conductive circuit (as, load) with do useful work then on negative electrode with described charged ion restructuring.The combination of positively charged and electronegative ion on negative electrode causes producing the free of contamination water as the accessory substance of reaction.
Polymer electrolyte fuel cells can be included in the polymer film (for example, proton exchange membrane (PEM)) all on both sides with catalyst electrode layer.The PEM of catalyst-coated can be positioned between a pair of gas diffusion media (GDM), and negative electrode and positive plate are placed on the outside of gas diffusion media layer.In manufacturing membrane electrode assembly process, catalyst electrode layer can be coated in each side of membrane carrier successively.That is, described layer is to adopt the sequential applications operation more lower one deck being applied in film support after a partially or completely dry layer to form.
Or, can use the diffusion media layers of catalyst-coated, wherein said catalyst is applied on gas diffusion media.In the process of dispersive medium of manufacturing catalyst-coating, catalyst electrode layer and ionomer layer can be coated in a side of base material successively.Be similar to manufacture polymer electrolyte fuel cells, use and comprise that the sequential applications operation more lower one deck being applied on membrane carrier after a partially or completely dry layer forms described layer.
Described manufacture method is complicated, consuming time and costliness.Comprising many layers, may there be considerable coating and drying equipment to repeat.In some cases, when wherein there is no drying steps ground coat between each coat, possible genetic horizon and/or disperse or dissolve the mixing of key component therein.In addition, can produce the layer heterogeneous with variable layer thickness.
Therefore, herein disclosed is the method for alternative fuel battery, membrane electrode assembly and manufacture membrane electrode assembly.
Summary of the invention
Embodiment disclosed herein is for to be applied to the method on base material by a plurality of fuel cell component coatings simultaneously.Described method comprises provides base material, and under laminar flow, two or more solution are coated on described base material simultaneously, non-porous layer solution is coated on the first porous layer solution simultaneously, and wherein said the first porous layer solution comprises electrode ink and described non-porous layer solution comprises coating solution.
Go back disclosed embodiment herein for a plurality of fuel cell component coatings are applied to the method on base material simultaneously.Described method comprises provides base material, with under laminar flow, three kinds or more kinds of solution are coated on described base material simultaneously, non-porous layer solution is coated on the first porous layer solution simultaneously, and wherein said the first porous layer solution comprises electrode ink and described non-porous layer solution comprises coating solution.
Also disclosed embodiment is the method for manufacture membrane electrode assembly herein.Described method comprises two or more solution is coated on the first base material to form cathode substrate simultaneously, wherein under laminar flow, carry out described coating, coating solution is coated in cathode solution simultaneously, two or more solution are coated on the second base material to form anode base material simultaneously, wherein under laminar flow, carry out described coating, coating solution is coated on anodic dissolution simultaneously, with described cathode substrate is hot-pressed onto to described anode base material, make negative electrode and anode at the opposite side of described film.
Particularly, the present invention relates to following aspect:
1. a plurality of fuel cell component coatings are applied to the method on base material simultaneously, described method comprises:
Base material is provided; With
Under laminar flow, two or more solution are coated on described base material simultaneously, non-porous layer solution is coated on the first porous layer solution simultaneously;
Wherein said the first porous layer solution comprises electrode ink and described non-porous layer solution comprises coating solution.
2. according to the method described in aspect 1, wherein said method further comprises porous enhancement layer is applied on described non-porous layer solution.
3. according to the method described in aspect 1, wherein said method further comprises that dry described the first porous layer solution and described non-porous layer solution are to form the first porous layer and non-porous layer.
4. according to the method described in aspect 2, wherein said method further comprises that dry described the first porous layer solution, described non-porous layer solution and described porous enhancement layer are to be formed on the first porous layer on described base material, non-porous layer on described the first porous layer and the described porous enhancement layer on described non-porous layer.
5. according to the method described in aspect 1, wherein use slit die coating process, swash plate coating process, curtain coating technique or print roll coating technique or its combination to apply described two or more solution simultaneously.
6. according to the method described in aspect 1, wherein said base material is gas diffusion media.
7. according to the method described in aspect 1, wherein said electrode ink comprises one or more solvents, ionomer and catalyst.
8. according to the method described in aspect 1, wherein said coating solution comprises one or more solvents and ionomer.
9. according to the method described in aspect 1, wherein said laminar flow has the Reynolds number that is less than approximately 50.
10. a plurality of fuel cell component coatings are applied to the method on base material simultaneously, described method comprises:
Base material is provided; With
Under laminar flow, three kinds or more kinds of solution are coated on described base material simultaneously, non-porous layer solution is coated on the first porous layer solution simultaneously;
Wherein said the first porous layer solution comprises electrode ink and described non-porous layer solution comprises coating solution.
11. according to the method described in aspect 10, wherein described the first porous layer solution is coated on microporous layers solution simultaneously, and described microporous layers is coated on described base material simultaneously.
12. according to the method described in aspect 10, and wherein said microporous layers solution comprises:
A. solvent, it comprises organic solvent, water or its mixture;
B. carbon granule; With
C. hydrophobic polymer, it comprises polytetrafluoroethylene, polyvinylidene fluoride, fluorinated ethylene propylene (FEP) or its combination.
13. according to the method described in aspect 11, and wherein said method further comprises that dry described microporous layers solution, described the first porous layer solution and described non-porous layer solution are to form microporous layers, the first porous layer and non-porous layer.
14. according to the method described in aspect 10, wherein the second porous layer solution is coated on described non-porous layer solution simultaneously, and wherein said the second porous layer solution comprises electrode ink.
15. according to the method described in aspect 14, and wherein said method further comprises that dry described the first porous layer solution, described non-porous layer solution and described the second porous layer solution are to form the first porous layer, non-porous layer and the second porous layer.
16. according to the method described in aspect 10, and wherein said base material is gas diffusion media.
17. according to the method described in aspect 10, and wherein said laminar flow has the Reynolds number that is less than approximately 50.
18. 1 kinds of methods of manufacturing membrane electrode assembly, described method comprises:
Two or more solution are coated on the first base material to form cathode substrate simultaneously, wherein under laminar flow, carry out described coating, coating solution is coated in cathode solution simultaneously;
Two or more solution are coated on the second base material to form anode base material simultaneously, wherein under laminar flow, carry out described coating, coating solution is coated on anodic dissolution simultaneously; With
Described cathode substrate is hot-pressed onto to described anode base material, makes negative electrode and the relative both sides of anode at described film.
19. according to the method described in aspect 18, and wherein said method further comprises dry described cathode substrate and described anode base material.
20. according to the method described in aspect 18, and wherein said laminar flow has the Reynolds number that is less than approximately 50.
Further feature and the advantage of the embodiment of the method for fuel cell, membrane electrode assembly and the manufacture membrane electrode assembly of describing herein will be set forth in the following detailed description, and they will become apparent to a certain extent or recognize by implementing the embodiment of (comprising detailed description, claims and accompanying drawing below) description herein to those skilled in the art by this explanation.
Aforementioned general remark and following detailed description have all been described various embodiments and have been intended to understand the character of claimed theme and characteristic provides general introduction or framework.Accompanying drawing is used for providing the further understanding to various embodiments, and is incorporated into and forms a part for specification.Accompanying drawing has illustrated the various embodiments of describing herein, and is used for explaining principle and the operation of claimed theme together with specification.
Accompanying drawing explanation
Fig. 1 has described the exemplary 2-layer while painting method according to the fuel cell component of the one or more embodiments that show and/or describe herein.
Fig. 2 has described according to the sectional view of the exemplary 2-layer fuel cell component of the method formation of Fig. 1.
Fig. 3 has described the exemplary 3-layer while painting method according to the fuel cell component of the one or more embodiments that show and/or describe herein.
Fig. 4 has described according to the sectional view of another exemplary 3-layer fuel cell component of the method formation of Fig. 3.
Fig. 5 has described the exemplary 3-layer while painting method according to the fuel cell component of the one or more embodiments that show and/or describe herein.
Fig. 6 has described according to the sectional view of another exemplary 3-layer fuel cell component of the method formation of Fig. 5.
Fig. 7 has described the exemplary 2-layer while painting method according to the fuel cell component of the one or more embodiments that show and/or describe herein.
Fig. 8 has described according to the sectional view of the exemplary 2-layer fuel cell component of the method formation of Fig. 7.
Fig. 9 has described the scanning electron micrograph of 2-tunic negative electrode cross section.
Figure 10 has described the scanning electron micrograph of 2-tunic anode cross section.
Figure 11 has described contrast according to the chart of the performance of the fuel cell of the one or more embodiments formation that show and/or describe herein.
Figure 12 has described the scanning electron micrograph of 3-layer microporous layers, film and negative electrode cross section.
Figure 13 has described contrast according to the chart of the performance of the fuel cell of the one or more embodiments formation that show and/or describe herein.
Figure 14 has described the scanning electron micrograph of 3-layer anode, film and negative electrode cross section.
Figure 15 has described the scanning electron micrograph of 2-tunic and negative electrode cross section.
Figure 16 has described the scanning electron micrograph of 2-tunic and anode cross section.
Embodiment
In more detail below with reference to while coating fuel cell components, to form the embodiment of the method for membrane electrode assembly and sub-component, the example shows in the accompanying drawings.In whole accompanying drawing, will with same Reference numeral, represent same or similar part as far as possible.
In order to describe and define the present invention, to note using term " substantially " to represent intrinsic degree of uncertainty herein, it can be owing to any quantity comparison, value, measurement or other signs.Also use term " substantially " to represent that quantity characterizes herein and can depart from described reference, and the degree that can not cause the basic function of main topic of discussion to change.
Herein disclosed is a plurality of fuel cell component coatings are applied to the method on base material simultaneously.Described method can be used to provide the one or more process modification in cost, performance, durability and manufacture efficiency.Have been found that applying two or more parts can be improved manufacture efficiency and be reduced manufacturing cost by the number of times reducing through coating machine simultaneously.In addition, can reduce component costs.Use parts solution, for example film ionomer solution, conventionally for example, than buying component parts (, the film of self-support) more cheap.Owing to less can reduce the possibility of extra defective workmanship by coating machine, and the startup reducing/close loss, so can also realize productive rate, improve.When described layer is applied directly to while causing more intimate between described layer and interface that combine closely on described coating material simultaneously, also can there is the improvement of durability and/or performance.Finally, coating functions layer can have cost advantage simultaneously, and what it can cause reduction is the required raw-material amount of performance requirement that meets.
As will be described in more detail below, described method generally includes provides base material, and two or more solution are coated on described base material simultaneously." solution " used herein represents true solution, dispersion and/or emulsion.
There are many combinations that can simultaneously be deposited on the possible solution on base material.Some examples, include, but are not limited to: be coated in film (non-porous layer) solution on electrode ink (or first porous layer solution) simultaneously; Be coated in the electrode ink (or first porous layer solution) on microporous layers solution simultaneously and be coated in the coating solution on described electrode ink film waterborne simultaneously; And be coated in film (non-porous layer) solution on electrode ink (or first porous layer solution) simultaneously and be coated in the second electrode ink (the second porous layer solution) on described coating solution simultaneously.Certainly, from described instruction, other combinations of deposit solution will be apparent for those of ordinary skills simultaneously, and can comprise, for example, use several layers of electrode, film or the microporous layers of painting method when describing herein.
With reference to Fig. 1, described under laminar flow, two coatings to be applied to simultaneously the illustrative methods (100) of base material.On the surface of base material (105), use coating die (130) to apply non-porous layer solution (115) and the first porous layer solution (110) simultaneously.Apply described coating solution, described non-porous layer solution is coated on described the first porous layer solution simultaneously.After applying described coating solution, described base material shown through drier (135) or a series of drier be dried described coating solution by removal of solvents, thereby form the base material (140) of coating.At described base material, through before drier, can optionally porous enhancement layer (133) be applied on described non-porous layer solution as the structure producing provides extra support.The example of applicable porous enhancement layer can include, but not limited to polymer film, woven wire, fabric or its combination.The example of applicable polymer film can comprise polytetrafluoroethylene (PTFE), expanded PTFE (ePTFE), polyvinylidene fluoride (PVDF) or fluorinated ethylene propylene (FEP) (FEP).
As further shown in Fig. 2, the base material of the coating that the illustrative methods by Fig. 1 forms comprises base material (105), is formed on the first porous layer (210) on this base material and is formed on the non-porous layer (215) on described the first porous layer (210).As mentioned above, optional enhancement layer (233) can be applied to non-porous layer (215).
In certain embodiments, apply coating solution and cathode solution simultaneously.In other embodiments, apply coating solution and anodic dissolution simultaneously.In forming membrane electrode assembly (MEA), can be dried described cathode portion and anode part and then their hot pressing/laminated together be formed to MEA.For dissimilar MEA, the pressure of described hot pressing/lamination and time can change.Before by hot pressing/lamination, extra layer (for example, ePTFE, subpad circle etc.) can be placed between described anode and negative electrode.
With reference to Fig. 3, described another illustrative methods (300).In this embodiment, method (300) is displayed under laminar flow three coatings is applied to base material simultaneously.On the surface of base material (305), use coating die (330) to apply microporous layers solution (320), the first porous layer solution (310) and non-porous layer solution (315) simultaneously.Apply described coating solution, described the first porous layer solution is coated on microporous layers solution and described non-porous layer solution is coated on described the first porous layer solution simultaneously simultaneously.After applying described coating solution, described base material shown through drier (335) or a series of drier be dried described coating solution by removal of solvents, thereby form the base material (340) of coating.Although do not describe, can be at described base material through before described drier, adding optional enhancement layer provides extra support for described base material.As further shown in Fig. 4, the base material of described coating comprises base material (305), form microporous layers (420) thereon, be formed on the first porous layer (410) in described microporous layers (420) and be formed on the non-porous layer (415) on described the first porous layer (410).
In certain embodiments, cathode solution, micropore solution and coating solution are applied on base material simultaneously.In other embodiments, anodic dissolution, micropore solution and coating solution are applied on base material simultaneously.In forming membrane electrode assembly (MEA), then described cathode portion and described anode part can be dried and by hot pressing/laminated together, to be formed MEA.
With reference to Fig. 5, described another illustrative methods (500).In this embodiment, method (500) is displayed under laminar flow three coatings is applied to base material simultaneously.On the surface of base material (505), use coating die (530) to apply the first porous layer solution (510), non-porous layer solution (515) and the second porous layer (525) simultaneously.Apply described coating solution, described non-porous layer solution is coated on described the first porous layer solution, and the second porous layer solution is coated on described non-porous layer solution simultaneously simultaneously.After applying described coating solution, described base material shown through drier (535) or a series of drier be dried described coating solution by removal of solvents, thereby form the base material (540) of coating.As further shown in Fig. 6, the base material of described coating comprises base material (505), form the first porous layer (610) thereon, be formed on the non-porous layer (615) on described the first porous layer (610) and be formed on the second porous layer (625) on described non-porous layer (615).
In some embodiments, cathode solution, coating solution and anodic dissolution are coated on base material simultaneously.For example, can apply three coatings simultaneously, make described negative electrode (or anode) solution on described base material, described coating solution is on described negative electrode (or anode) solution, and described anode (or negative electrode) solution is on described coating solution.In order to form MEA, the second base material (for example, gas diffusion media) can be affixed to the top layer of described three-decker, and relative with described the first base material.In this embodiment, the second base material can be affixed to described anode (or negative electrode) layer to form MEA.
With reference to Fig. 7, described another illustrative methods (700).In this embodiment, method (700) is displayed on and under laminar flow, two coatings is applied to applique (decal) base material simultaneously.Described applique base material is a kind of chemically stable, smooth, smooth non-porous base material, on it, can apply coating, but this coating is removed from described applique base material in the subsequent step in method subsequently.Applique base material is not used in formation membrane electrode assembly.On the surface of described applique base material (705), use coating die (730) to apply the first porous layer solution (710) and non-porous layer solution (715) simultaneously.Apply described coating solution, described non-porous layer solution (715) is coated on described the first porous layer solution (710) simultaneously.Can add optional enhancement layer (733) take before described base material passes drier as described structure provides extra support.After applying described coating solution, the layer of coating (710,715) is shown through cure/dry (735) district to remove the base material (740) that is included in the part or all of solvent in described floor and forms coating.Then, laminated sheet (745) is separated with base material (705), the layer that described laminated sheet is described coating (710,715 and optionally 733).In certain embodiments, separated with base material (705) by peeling off laminated sheet (745).Optionally, then can make laminated sheet (745) through drier (750) or a series of drier to be dried described laminated sheet by complete removal of solvents.As further shown in Fig. 8, laminated sheet (745) comprises the first porous layer (810), is formed on the non-porous layer (815) on described the first porous layer (810) and is formed on the optional enhancement layer (833) on described non-porous layer (815).Under instruction herein, other treatment steps will be apparent to those skilled in the art.Only as an example, the method for describing can be with the various combination of porous and non-porous layer by two, three, four, five etc. or more multi-layered being coated on base material or applique base material simultaneously.
In certain embodiments, coating solution and cathode solution are coated on described applique base material simultaneously, are then dried to form cathode portion.In other embodiments, coating solution and anodic dissolution are coated on described applique base material simultaneously, are then dried to form anode part.In forming membrane electrode assembly (MEA), described cathode portion and described anode part can by together with hot pressing to form MEA.After hot pressing, can peel off described applique from described electrode, and it is upper to form composite component gas diffusion media can be placed on to described anode and negative electrode.Optionally, can apply as required subpad circle.
In certain embodiments, before can forming non-porous layer on described the first porous layer, described the first porous layer and viscosity ionomer layer (not shown) are deposited in described base material or described microporous layers simultaneously.Because described the first porous layer and described non-porous layer all comprise ionomer, viscosity ionomer layer can provide better contact and/or adhere between described the first porous layer and described non-porous layer.Bound by theory, not it is believed that described viscosity ionomer layer can reduce the contact resistance between described the first porous layer and described non-porous layer, and increases the proton exchange between described the first porous layer and described non-porous layer.It all can improve fuel battery performance.In one embodiment, described ionomer layer is the mixture of ionomer and methyl alcohol; But, other ionomer solutions can be same being applicable to.Described ionomer layer can provide good ionomer contact between described the first and second porous layers and described non-porous layer.
While painting method disclosed herein can be used for forming membrane electrode assembly as above (MEA).The MEA forming according to one or more embodiments of describing herein can be clipped between two bipolar plates (BPP) to form fuel cell.The term bipolar plates that the art is used, also comprises unipolar plate.Described plate can conduct electricity, and, in certain embodiments, can be made by carbon composite, metal or coated metal material.In some embodiments, fuel cell pack comprises that many and bipolar plates replaces stacking MEA.In some embodiments, described fuel cell pack can have at least about 1000 hours, at least about 1500 hours or at least about the heap durability of 2000 hours.In other embodiments, described fuel cell pack can have the heap durability lower than approximately 7000 hours, 6000 hours or 5000 hours.
Can use slit die coating process, swash plate coating process, curtain coating technique or its combination to apply described coating solution simultaneously.In slit die coating process, can use and there is the coating die of two or more slits so that different coating solutions passes each slit.In swash plate coating process, use swash plate coating die to apply two or more coating solutions simultaneously.Swash plate coating die forms two or more liquid level compounds (that is, one deck is on another layer), and it flows down coating die swash plate surface, crosses coating die lip surface and flows on described base material.In curtain coating technique, liquid flows out from slit, and falls under gravity (being called heavy curtain) to the base material moving horizontally.Be similar to swash plate coating process, heavy curtain can be two or more liquid level compounds.Drier or a series of drier can comprise that infared dryer, hot air dryer or other are applicable to the drier of dry a plurality of coating solution layers.
Have been surprisingly found that, in using method disclosed herein, two or more solution can be applied to base material simultaneously, in deposition with after being dried, still keep the obvious ATM layer relationsATM between coating simultaneously.In addition, have been surprisingly found that, when two or more solution that comprise solvent and little solid particle are coated on base material simultaneously, can apply two or more coating solution layers simultaneously, and on the interface of described layer, significantly do not mix or pollute.For example, non-porous layer is being coated in to the place on porous layer simultaneously, is shockingly finding, described porous (below) layer is not mixed or pollutes by described non-porous (above) layer.Do not wish bound by theory, it is believed that in order to obtain obvious ATM layer relationsATM in coating procedure at the same time, should be in conjunction with described coating solution under laminar flow conditions.
For use previously general introduction a plurality of layers of paint-on technique time deposition, for fear of layer, mix, the flow regime of every one deck is stratiform.The mixing of described film and electrode layer may cause the direct short-circuit of battery because in MEA each electrode will with another close contact.Reynolds number in the slit of mould is used to assess the degree of laminar flow.In certain embodiments, Reynolds number is less than approximately 2100 to keep obvious layer.In other embodiments, Reynolds number is less than approximately 50 to keep obvious layer.In another embodiment, Reynolds number is less than approximately 10 to keep obvious layer.Reynolds number is nondimensional, and can calculate as follows:
Wherein cm/sec; ,
cm; With , g/cm-sec.
In addition, it is believed that solvent and/or the solids content optimized for coating solution can prevent the remarkable diffusion between coating solution layer.For example, can change the solvent ratios of solution and/or solid concentration to avoid layer diffusion.For example, if the content of alcohol or water is too high or too low with respect to other in certain layer, can cause remarkable diffusion and/or the mixing of described layer.Wherein the solids content in certain one deck is significantly different from the place of the solids content in adjacent layer, also there will be remarkable diffusion and/or the mixing of described layer.Diffusion between described layer can cause coating unstable, causes that described layer is repelled and/or cause the thickness evenness that is difficult to accept differ from mutually.The place that excess diffusion occurs, can produce component migration, and the fragment of wherein one or more layers is diffused in one or more other layers in coating structure.Conventionally, component migration can affect performance and/or the durability of the final electrode assemblie (" UEA ") using.By UEA, we represent film, electrode and dispersive medium as a unit with, for example, the assembly of miscellaneous part (as subpad circle and bipolar plates etc.).
base material
Applicable base material can comprise, but be not limited to, dispersive medium (DM), gas diffusion media (GDM) and non-porous base material, as polymer film (as, polyvinylidene fluoride (PVDF), fluorinated ethylene propylene (FEP), polypropylene, polyimides, polyester or polytetrafluoroethylene (PTFE)), the paper (for example, the paper of polyurethane-coated) of polymer-coated, silicon release liners, metal forming (for example, aluminium foil), metallic support (for example, stainless steel support), there is wheel or other non-porous material of chrome coating.DM and GDM can comprise carbon back base material, as carbon paper, carbon fabric or cloth, the non-carbon fibre web of knitting, its be high-voidage and with electrode accessibility well, provide reacting gas.The carbon back material can be used in enforcement of the present invention can comprise: Toray carbon paper, SpectraCarb carbon paper, non-carbon cloth, Zoltek carbon cloth, the Zoltek PWB-3 etc. of knitting of AFN.Also can be with allowing hydrophobic assembly or the microporous layers of removing water from fuel cell to process DM and GDM.According to them, in the MEA of appointment, will be built in which side, DM can be become to Anodic Type GDM or cathode type GDM with GDM custom-made.In certain embodiments, porous substrate can have the thickness of approximately 100 microns-Yue 500 microns.In other embodiments, porous substrate can have the thickness of approximately 150 microns-Yue 300 microns.In certain embodiments, non-porous matrix can have the thickness of approximately 10 microns-Yue 3200 microns.In other embodiments, non-porous base material can have the thickness of approximately 20 microns-Yue 40 microns.
non-porous layer solution
Described non-porous layer solution comprises coating solution.Described coating solution can comprise any applicable polymer dielectric.Available polymer dielectric in the present invention can be highly fluorinated and, in certain embodiments, fluoridized, but can be also partially fluorinated or nonfluorinated.The example of available fluorinated polymer electrolyte in the present invention can comprise copolymer, tetrafluoroethene-fluroxene copolymer, perfluorinated sulfonic acid (PFSA), Freon C318 (PFCB) or its mixture of tetrafluoroethene and one or more sour official's energy comonomers of fluoridizing.Described ionomer material is used with fluid composition, that is, dissolve or be dispersed in applicable solvent.Can obtain many fluorine-containing ionomer materials with the form of the aqueous solution of various concentration.The ionomer content of described solution can be the 5-30wt% of described solution.Certainly, also can use the ionomer material providing with water-borne dispersions form.This dispersion can comprise, for example, and the Nafion PFSA polymeric dispersions of being sold by DuPont.The example of operable floride-free ionomer material can comprise polybenzimidazoles, SPSF and the sulfonated polystyrene of hydrocarbon polymer, sulfonated polyether ketone, aryl ketones, acid doping.Generally described film can be coated on base material, the wet thickness that makes described rete is approximately 50 μ m-approximately 150 μ m.In certain embodiments, the rete being formed by described method can have the dry thickness of approximately 3 μ m-approximately 50 μ m.In certain embodiments, the rete being formed by described method can have the dry thickness of approximately 4 μ m-approximately 30 μ m.
Described rete can be used has 1200 or less, in certain embodiments 1100 or less, in other embodiments 1000 or less, in a further embodiment 900 or less, and in embodiment further 800 or less, the ionomer of equivalent.Ionomeric " equivalent " (EW) represent in and the needed ionomeric weight of alkali of monovalent.In certain embodiments, described film can comprise the ionomeric blend with different EW.
In certain embodiments, can after drying steps, to described rete, anneal to help to obtain necessary durability.Rete also can be from using optional enhancement layer to benefit to improve the mechanical strength of described film, so that be difficult for occurring the fault with pressure correlation.The example of applicable enhancement layer comprises expanded PTFE (ePTFE), woven wire, fabric and for apparent other the applicable materials of those of ordinary skills.In certain embodiments, described film and described enhancement layer can by together with anneal.In other embodiments, described electrode, film and enhancement layer can by together with anneal.Annealing can comprise the temperature that described film is heated above to its glass transition temperature, then Slow cooling it to form the domain be the arrangement that can give described film Rigidity and strength.
When standing the chemical environment occurring in typical PEM fuel cell, amberplex can be degraded in time.The mechanism that ionic conductive polymer membrane can be degraded is the fluorine loss by under open circuit voltage (OCV) and the dry run condition at high temperature (that is, fluoride discharge).May contribute to the another kind mechanism of the degraded of ionic conductive polymer membrane is described film and active species, as hydrogen peroxide and hydroxyl radical free radical, reaction.In order to reduce membrane degradation, may require to use chemical degradation moderator.The applicable chemical degradation moderator that suppresses depolymerization can comprise cerium-containing compound, contains manganese compound and contain porphyrin compound.In one embodiment, described moderator comprises Pt nanoparticle, CeO 2or MnO 2.Other applicable examples can comprise the solubility sulfonate (SO of any or its combination in following metal ion 3 2), sulfate (SO 4 2), carbonate (CO 3 2) or nitrate (NO 3 2): Co 2+, Co 3+, Fe 2+, Fe 3+, Mg 1+, Mg 2+, Mn 1+, Mn 2+, Mn 3+, Cl Mn 3+, HO Mn 3+, Cu 1+, Cu 2+, Ni 1+, Ni 2+, Pd 1+, Pd 2+, Ru 1+, Ru 2+, Ru 4+, Vn 4+, Zn 1+, Zn 2+, Al 3+, B, Si (OH) 2 2+, Al 3+, HOIn 3+, Pb 2+, Ag +, Sn 2+, Sn 4+, Ti 3+, Ti 4+, VO +, Pt 2+, Ce 3+or Ce 4+.
porous layer solution
In order to form loose structure in porous (as, electrode) and/or microporous layers, wherein on one or more porous solution layers, formed non-porous solution layer simultaneously, air must infiltrate described porous solution layer.Wherein said base material is DM or GDM, itself is loose structure, and described DM or GDM can fill solution electrode and/or micropore solution for air provides path, make to form porous and microporous layers when dry.Base material is the place of non-porous substrate, does not have the obvious path for porous described in Air infitration and/or micropore solution.Yet, be surprised to find that, non-porous and porous electrode solution layer are coated to simultaneously to the independently layer structure that has caused having obvious pore structure on non-porous base material in described electrode.Bound by theory not, it is believed that and in the drying steps process as shown in Fig. 1,3,5 and 7, discharge the air that is dissolved in porous electrode/micropore solution to form porous electrode layer.
Described porous layer solution can comprise electrode ink, and it can be used for forming cathode layer or anode layer.Described electrode ink comprises solvent, ionomer and catalyst.Can to form catalyst solution, prepare described electrode ink by catalyst being added to solvent with abrasive media together with ionomer in bottle.Then, can pass through, for example, the bottle that described catalyst solution is housed is placed on ball mill and under the existence of abrasive media and rotate this bottle, grind described catalyst solution.
In enforcement of the present invention, can use any applicable catalyst.In certain embodiments, described catalyst can be for being coated to the catalyst metals on conductive carrier surface.Conventionally, use the catalyst granules of carbon load.The catalyst granules of carbon load is the carbon of about 50-90wt% and the catalyst metals of about 10-50wt%.Described catalyst can be for having the fine noble metal of catalytic activity.Applicable noble metal includes, but not limited to platinum group metal, as platinum, palladium, iridium, rhodium, ruthenium and alloy thereof.
Described solvent can comprise isopropyl alcohol, methyl alcohol, ethanol, normal propyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, water, 2-methyl-2-butanols, 2-methyl-2-amylalcohol, 2,3-dimethyl-2-butanols, 2,3-dimethyl-2,3-butanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-2,4-hexylene glycol, 2,5-dimethyl-2,5-hexylene glycol, 3-hydroxy-3-methyl-2-butanone and 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and composition thereof.Described solvent can be with the 1-90wt% of described electrode ink, 5-80wt% in certain embodiments, 10-50wt% in another embodiment, amount be present in described ink.
Described electrode ink comprises ionomer material, and it can be identical or different with the ionomer material for non-porous layer solution.Applicable ionomer material comprises, but be not limited to polybenzimidazoles, SPSF, sulfonated polystyrene and its mixture of the copolymer of tetrafluoroethene and one or more sour official's energy comonomers of fluoridizing, tetrafluoroethene-fluroxene copolymer, perfluorinated sulfonic acid (PFSA), Freon C318 (PFCB), hydrocarbon polymer, sulfonated polyether ketone, aryl ketones, acid doping.Conventionally, the ionomer material in described ink should be used with fluid composition, that is, dissolve or be dispersed in applicable solvent.The form of the aqueous solution that can various concentration obtains many fluorine-containing ionomer materials.The ionomer content of described solution can described solution the 5-30wt% of weight.Certainly, also can use the ionomer material providing with water-borne dispersions form.This dispersion can comprise, for example, and the Nafion PFSA polymeric dispersions of being sold by DuPont.As further described in detail below, the ionomer material in described ink can be low EW ionomer, high EW ionomer or the blend with the ionomer material of high EW and low EW.
As mentioned above, by catalyst, the form with catalyst ink is applied on base material.Described catalyst ink can comprise the dispersion of the catalyst granules on carbon carrier in ionomer dispersion.Described ink can comprise 5-30% solid (that is, ionomer and catalyst) and, in certain embodiments, can comprise the solid of 10-20%.In certain embodiments, being included in solid in described ink, to have diameter be the granularity of approximately 0.01 micron-Yue 15 microns.In other embodiments, being included in solid in described ink, to have diameter be the granularity of approximately 0.1 micron-Yue 10 microns.In certain embodiments, the solid being included in described ink also can have such particle size distribution: it is the granularity of approximately 0.01 micron-Yue 15 microns that at least 80% described solid has diameter.In certain embodiments, the solid being included in described ink also can have such particle size distribution: it is the granularity of approximately 0.01 micron-Yue 10 microns that at least 80% described solid has diameter.In other embodiments, the solid being included in described ink also can have such particle size distribution: it is the granularity of approximately 0.01 micron-Yue 15 microns that at least 90% described solid has diameter.In certain embodiments, the solid being included in described ink also can have such particle size distribution: it is the granularity of approximately 0.01 micron-Yue 10 microns that at least 90% described solid has diameter.
Other additives, as adhesive, cosolvent, antimitotic agent (crack reducing agent), wetting agent, defoamer, surfactant, anti-settling agent, anticorrisive agent, pore creating material, even paint, stabilizer, pH adjusting agent, grinding aid and other materials, can be used in described catalyst ink water composition to improve coating character.In addition, can add alkalinity additive, as NaOH (NaOH) or potassium hydroxide (KOH) cushion as described in ionomeric acidic-group.
In certain embodiments, antimitotic agent is added in described catalyst electrode ink.The electrode of being made by catalyst ink can form fracture network on described surface, and it is called as " be full of cracks ".It is believed that " be full of cracks " is because the stress producing occurs when wet film is dry and solid material starts to merge.Do not wish bound by theory, the stress gradient that described crack can cause due to the local thickness's difference in wet film forms.Described crack also can form due to the inherent shortcoming of electrode after dry.Described electrode is formed by the porous matrix being supported by described ionomer (it the is a kind of relatively weak adhesive) carbon of combination.As a result, the matrix of described carbon carrier provides minimum enhancing for described ionomer, and the matrix producing possibly cannot be born a large amount of stress in dry described catalyst ink process, causes in operation of fuel cells process, there is larger Opportunity formation crack.If the tensile strength of described film is enough to overcome the drying stress causing, can form the stress that described film is alleviated in be full of cracks.Thus, antimitotic agent can be added to and in catalyst electrode ink, prevent from forming be full of cracks.
The example of applicable antimitotic agent can comprise, but be not limited to, the relatively high boiling solvent adding, for example, diacetone alcohol, carbon fiber, nano clay small pieces are (for example, can be from Southern Clay Product of Gonzales, TX obtains), or low equivalent weight ionomer and the ionomeric mixture of high equivalent weight or its combination.Diacetone alcohol can exist with the amount up to about 30wt% of negative electrode ink.Described carbon fiber can have the length of about 10-20 micron and the diameter of 0.15 μ m.Described carbon fiber can be with about 1:6(w/w) fiber: the ratio of catalyst exists.In addition, as above disclosed, described catalyst ink comprises ionomer material.The mixture of low equivalent (being less than about 800EW) ionomer or low equivalent weight ionomer and high equivalent weight ionomer (being greater than 800EW) can be used for relaxing the generation of be full of cracks.In certain embodiments, described ionomer material can be for having the ionomeric mixture that is greater than approximately 850 high equivalent weight and be less than approximately 750 low equivalent.
microporous layers solution
Described microporous layers is in fuel cell, to be used for from cathod catalyst and the excessive aqueous water of diffusion layer interface sucking-off, and is used for providing the porous layer of improvement in performance under wet practice condition.Can add using it as discrete layer the one or both sides of dispersive medium base material to.Described microporous layers solution is generally the dispersion of the various blends that comprise carbon granule, hydrophobic polymer and solvent.Term " carbon granule " is used for describing the carbon (longest dimension of any particle, for being compatibly less than 500 μ m, is less than 300 μ m, is less than 50 μ m) of any fine form, comprises carbon dust, carbon thin slice, carbon nano-fiber or microfibre and fine-grain graphite.Carbon granule can be carbon black pellet.The example of applicable hydrophobic polymer can comprise polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), fluorinated ethylene propylene (FEP) (FEP) or other organic or inorganic hydrophobic polymer material.Described carbon granule and hydrophobic polymer can be dispersed in liquid, and it can be, for example, and organic solvent, water and its mixture.In certain embodiments, described solvent can comprise isopropyl alcohol, methyl alcohol, ethanol, normal propyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, water, 2-methyl-2-butanols, 2-methyl-2-amylalcohol, 2,3-dimethyl-2-butanols, 2,3-dimethyl-2,3-butanediol, 2,4-dimethyl-2,4-pentanediol, 2,4-dimethyl-2,4-hexylene glycol, 2,5-dimethyl-2,5-hexylene glycol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and composition thereof at least one of them.As shown in FIG. 3, described microporous layers solution and other coating solutions can be applied in gas diffusion media layer simultaneously.
For useful microporous layers in application at the same time, adjust and/or control the various performances of described composition, as granularity, grain density, binder dosage, porosity, pore-size distribution and layer thickness, may be useful.In certain embodiments, the microporous layers forming after dry described microporous layers solution can comprise the carbon granule of about 50%-90% and the hydrophobic polymer of about 10%-45%.Described microporous layers can be thick for 2 μ m-100 μ m, and 10 μ m-70 μ m are thick in certain embodiments.The porosity of described microporous layers can compatibly be greater than 50%, and in certain embodiments, is greater than 70%.The aperture of described microporous layers can covering wide scope, for example 5 nm-10 μ m.
Can further illustrate the embodiment of describing herein by following non-limiting example.
Embodiment
Unless outside indicating especially, used in all embodiments the 2-layer slit die moving with respect to base material.By gravimetric analysis, determine the catalyst loadings of electrode.Use film cross section to measure film thickness by scanning electron microscopy (SEM).By infrared drying, be dried the element applying.Wherein note, before there is a large amount of being dried, expanded PTFE (ePTFE) is attached to wet film.
Embodiment 1
mEA of the present invention
By the spherical zircite abrasive media of the Pt alloy catalyst of 6.02 gram 30% (being provided by Tanaka Kikinzoku International) and 600 grams 5 millimeters being added in the polyethylene bottle of first 250ml, prepare negative electrode ink.In the polyethylene bottle of second 250ml, by the ionomer (solid of 20.5wt.%, the water of 79.5wt.%) of the ionomer of 10.1 gram of 900 equivalent (EW) (water of the solid of 28wt.%, the ethanol of 42wt.%, 30wt.%) and 4.53 grams of 700EW, with together with the solution of 34.11 grams of ethanol, 19.33 grams of water and 0.89 gram of oleyl amine that comprises 26.7wt.%, the normal propyl alcohol of 55wt.% and the water of 18.3wt.%, add in described second bottle.Stir contained thing approximately 15 minutes.Then, the ionomer solution from described second bottle is added in the catalyst and abrasive media in described first bottle.Then, described first bottle is placed on ball mill and with 125 RPM rotation 72 hours.
By 104.7 grams of ionomer dispersion (DuPont Nafion D2020, the normal propyl alcohol of the solid of 21.4wt.%, the water of 33.1wt.% and 45.5wt.%), 44.1 grams of normal propyl alcohols and 11.2 grams of water being added in the polyethylene bottle of 250 milliliters, prepare nonporous membrane solution.Make described solution mix a whole night.
At a slice GDM(, by Freudenberg FCCT KG, provided) surface on, under laminar flow, described nonporous membrane solution and negative electrode ink are coated on described GDM base material simultaneously, described non-porous rete is coated on described negative electrode ink to form wet composite construction simultaneously.The wet-film thickness of described negative electrode ink layer is 92 microns, and has 0.2 milligram of Pt/cm 2load capacity.The wet-film thickness of described rete is 113 microns, and has the dry thick of about 7-9 micron.Apply described two-layer after and occurring any be dried in a large number before, by a slice ePTFE(Donaldson D1326) be placed on described wet film surface.After applying ePTFE, then allow the standing 10-30 of described wet composite construction second described ePTFE to be sucked in described coating solution completely.Then, under the infrared lamp of source temperature with 450 ℉, dry described wet composite construction has base material to form in approximately 10 minutes, is formed on the negative electrode on described base material and is formed on the dry composite construction of the nonporous membrane on described negative electrode.
By 6.62 grams of spherical zircite abrasive medias containing the graphitization Vulcan catalyst (being provided by Tanaka Kikinzoku International) of 20%Pt and 520 grams 5 millimeters being added in the polyethylene bottle of first 250ml, prepare anode ink.In the polyethylene bottle of second 250ml, add the ionomer (water of the solid of 28wt.%, the ethanol of 42wt.%, 30wt.%) of 22.53 gram of 900 equivalent (EW), 20.75 grams of ethanol, 13.72 grams of water and 1.39 grams of solution containing the water of the oleyl amine of 26.7wt.%, the normal propyl alcohol of 55wt.% and 18.3wt.%, and stir contained thing 15 minutes.Then, the ionomer solution from described second bottle is added in the catalyst and abrasive media in described first bottle.Then, described first bottle is placed on ball mill and with 125 RPM rotation 72 hours.Identical nonporous membrane solution for above-mentioned negative electrode ink is also used to described anode ink.
At a slice GDM(, by Freudenberg FCCT KG, provided) surface on, under laminar flow, described nonporous membrane solution and anode ink are coated on described GDM base material simultaneously, described non-porous rete is coated on described anode ink water layer to form wet composite construction simultaneously.The wet-film thickness of described anode ink water layer is 25 microns, and has 0.05 milligram of Pt/cm 2load capacity.The wet-film thickness of described film is 113 microns, and has the dry thick of about 7-9 micron.Then, described wet composite construction is placed on and within the infrared lamp of the source temperature with 450 ℉ approximately 10 minutes, to form, there is base material, be formed on the anode on described base material and be formed on the dry anode composite structure of the nonporous membrane on described anode.
Described negative electrode composite construction and described anode composite structure are by together with hot pressing and form MEA of the present invention.
contrast MEA
Also prepared contrast MEA.In order to form described contrast MEA, by the spherical zircite abrasive media of the Pt alloy catalyst of 6.02 gram 30% (being provided by Tanaka Kikinzoku International) and 300 grams 5 millimeters being added in the polyethylene bottle of first 250ml, prepare negative electrode ink.In the polyethylene bottle of second 250ml, with 35.68 grams of positive acetone, 8.1 grams of water with 1.47 grams containing the ionomer (water of the solid of 28wt.%, the ethanol of 42wt.%, 30wt.%) that adds 23.8 grams of 900EW together with the solution of the water of the oleyl amine of 26.7wt.%, the normal propyl alcohol of 55wt.% and 18.3wt.%.Stir contained thing approximately 15 minutes.Then, the ionomer solution from described second bottle is added in the catalyst and abrasive media in first bottle.Then, described first bottle is placed on ball mill and with 125 RPM rotation 24 hours.
In forming described contrast MEA, also by the spherical zircite abrasive media of the Pt graphitization Vulcan catalyst (being provided by Tanaka Kikinzoku International) of 6.41 gram 20% and 500 grams 5 millimeters being added in the polyethylene bottle of first 250ml, prepared anode ink.In the polyethylene bottle of second 250ml, add the ionomer (water of the solid of 28wt.%, the ethanol of 42wt.%, 30wt.%) of 16.07 gram of 900 equivalent (EW), 78.87 grams of ethanol, 23.65 grams of water, and stir contained thing 15 minutes.Then, the ionomer solution from described second bottle is added in the catalyst and abrasive media in described first bottle.Then, described first bottle is placed on ball mill and with 125 RPM rotation 24 hours.
On the surface of separated GDM sheet (being provided by Freudenburg FCCT KG), use Meyer rod (Mayer rod) respectively with 0.05 and 0.20 milligram of Pt/cm 2final load capacity apply described anode ink and negative electrode ink.The ionomer solution of 5wt.% is sequentially coated on each electrode to 0.16 milligram of ionomer/cm 2final load capacity.The film (being provided by W.L. Gore & Associates) that a slice is had to the thickness of 18 microns is placed between described two electrodes and hot pressing contrasts MEA to form.
With reference to Fig. 9 and 10, what describe is the cathode composite of formation and the scanning electron micrograph of anode composite material.Fig. 9 has shown according to the method for the present invention of describing in embodiment 1 and has been formed on negative electrode (910), film (915) and the ePTFE layer (933) on base material (905).Figure 10 has shown according to the method for the present invention of describing in embodiment 1 and has been formed on anode (1010) and the rete (1015) on base material (1005).
The multi-layer fuel cell (SML MEA) that Figure 11 has applied when having described embodiments of the invention 1 and 50 cm that contrast MEA 2life-span starting point (BOL) fuel battery performance.Under identical operating condition, test described SML MEA and contrast MEA.BOL test relates to described SML MEA and the contrast MEA polarization curve test of (for example, temperature, relative humidity (RH), Chemical Measurement compare etc.) under different operating conditions.As shown in Figure 11, described SML MEA and described contrast MEA performance are good equally.
embodiment 2
By by the spherical zircite abrasive media of 480 grams 5 millimeters, 10.29 grams of Superior Graphite Grade PureBlack SCD205-110 and 2.06 grams of Ultraflon 8TA PTFE(sintering 45 minutes under the condition of 300 ℃) add in the polyethylene bottle of 500ml and shake contained thing a few minutes and prepare microporous layers solution.In described bottle, add 55.86 grams of water, 31.0 grams of normal propyl alcohols, 11.44 grams of 1M HNO 3and 9.35 grams of ionomers (DuPont Nafion DE2020, the solid of 21.4wt.%, the normal propyl alcohol of the water of 33.1wt.% and 45.5wt.%), and be placed on ball mill with 125 RPM rotation 24 hours.
By preparing described negative electrode ink in the polyethylene bottle that adds first 500ml to containing the graphitization Vulcan C catalysts (being provided by Tanaka Kikinzoku International) of 50%Pt and 520 grams of 5 millimeters of spherical zircite abrasive medias by 16.89 grams.In second bottle, add 10.7 grams of positive acetone, 39.0 grams of diacetone alcohols and 4.8 grams of water, and thoroughly mix contained thing.This solution in described second bottle is added in the catalyst and abrasive media in described first bottle, and shake contained thing to soak described catalyst.58.6 grams of ionomer solutions (DuPont Nafion DE2020, the solid of 21.4wt.%, the normal propyl alcohol of the water of 33.1wt.% and 45.5wt.%) are added in described first bottle and this bottle is placed on ball mill, with 145 RPM rotation 24 hours.
Normal propyl alcohol by the solid of DuPont Nafion DE2020(21.4wt.%, the water of 33.1wt.% and 45.5wt.%) provide described coating solution.
At a slice GDM(, by Freudenburg FCCT KG, provided) surface on, use three layers of slit die under laminar flow, described micropore solution, negative electrode ink and coating solution to be coated on described GDM base material to form wet composite construction simultaneously.Apply simultaneously, described negative electrode ink is coated on microporous layers solution, and described coating solution is coated on described negative electrode ink simultaneously simultaneously.Then, there is under the source temperature infrared lamp of 450 ℉ dry described wet composite construction approximately 10 minutes to form the composite construction that there is base material, is formed on the microporous layers on described base material and is formed on the negative electrode in described microporous layers and be formed on the nonporous membrane on described negative electrode.
The wet-film thickness of described microporous layers is 154 microns, and causes approximately 25 microns dry thick.The wet-film thickness of described negative electrode is 62 microns, and causes 0.4 milligram/cm 2pt load capacity.The wet-film thickness of described film is 85 microns, causes approximately 10 microns dry thick.Then, under the IR lamp of source temperature with 400 ℉ dry described wet 3-layer structure approximately 10 minutes to form dry negative electrode composite construction.Can in Figure 12, can see the scanning electron micrograph of described dry negative electrode composite construction, it has shown the microporous layers (1220) that is formed on base material (1205), has been formed on the cathode layer (1210) in described microporous layers (1220) and is formed on the rete (1215) on described cathode layer (1210).
As prepared anode ink described in embodiments of the invention 1 above.It is identical with the coating solution that uses that described coating solution is prepared together with described negative electrode ink with this.At a slice GDM(, by Freudenburg FCCT KG, provided) surface on, use 2-layer slit die under laminar flow, described anode ink and coating solution to be coated on described GDM base material to form wet composite construction simultaneously.Apply simultaneously, make described anode ink be coated in described GDM upper simultaneously, and that described coating solution is coated in described anode ink is waterborne simultaneously.Then, under the infrared lamp of source temperature with 450 ℉ dry described wet composite construction approximately 10 minutes to form dry anode composite structure.
Figure 13 has described the contrast of the sample of the present invention of embodiment 2 and the typical polarization curve of comparative sample.Under 80 ℃, 32% relative humidity and 150 kPa absolute pressures, move the sample of the present invention of embodiment 2.Described comparative sample is as made in embodiment 1.Measuring voltage and alternating-current resistance (HFR) under various current densities.As shown in the figure, the fuel cell of the present invention of embodiment 2 and the performance of described comparison fuel cell are same good.
embodiment 3
By 3-layer slit die, negative electrode, film and anode layer being coated to a slice GDM(is simultaneously provided by Freudenburg FCCT KG) upper to form wet composite construction.Under laminar flow, apply simultaneously, described coating solution is coated on described negative electrode ink, and described anode ink is coated on described coating solution simultaneously simultaneously.Then, under the infrared lamp of source temperature with 450 ℉ dry described wet composite construction approximately 10 minutes to form dry composite construction.Figure 14 described to have base material (1405), be formed on negative electrode (1410) on described base material (1405), be formed on the nonporous membrane (1415) on described negative electrode (1410) and be formed on the SEM of the dry composite construction of the anode (1420) on described nonporous membrane (1415).
Described negative electrode and anode ink have been used identical formula and have been by containing the Vulcan catalyst (being provided by Tanaka Kikinzoku International) of 50%Pt, 3.37 grams of carbon fibers (by Showa Denko Carbon by 22.22 grams, Inc. provide, 10-20 micron is long, 0.15 micron wide) and the spherical zircite abrasive media of 1360 grams 5 millimeters add to and prepare in the polyethylene bottle of 500ml.In an independent bottle, added 76.26 grams of ionomer solutions (DuPont Nafion DE2020, the normal propyl alcohol of the solid of 21.4wt.%, the water of 33.1wt.% and 45.5wt.%), the oleyl amine solution of 61.26 grams of normal propyl alcohols, 6.74 grams of water and 3.52 grams of 26.7wt.%, and stir contained thing approximately 15 minutes.Described ionomer solution is added in catalyst, carbon fiber and the abrasive media in described first bottle.First bottle is placed on to upper 96 hour of ball mill with 145 RPM rotations.Described coating solution is DuPont Nafion DE2020 (normal propyl alcohol of the solid of 21.4wt.%, the water of 33.1wt.% and 45.5wt.%).
Apply described anode and cathode layer to there is identical wet-film thickness and Pt load capacity.The wet-film thickness of described anode and cathode layer is 65 microns, causes for 0.4 milligram of Pt/cm of each electrode 2load capacity.The wet-film thickness of described film is 122 microns, causes the name of 14 microns dry thick.Then lower 10 minutes of the IR lamp that described 3-layer structure is placed on to the source temperature with 500 ℉ is to form dry composite construction.
embodiment 4
By 2-layer slit die, described electrode and rete are coated on non-porous thin polymer film (polyimide film of 1.2 millimeters of being manufactured by DuPont) simultaneously.By containing the Vulcan catalyst (being provided by Tanaka Kikinzoku International) of 50%Pt, 1.82 grams of carbon fibers (by Showa Denko Carbon by 11.88 grams, Inc. provide, 10-20 micron is long, 0.15 micron wide) and the spherical zircite abrasive media of 800 grams 5 millimeters add in the polyethylene bottle of first 500ml.In the polyethylene bottle of second 500ml, add the ionomer (water of the solid of 28wt.%, the ethanol of 42wt.%, 30wt.%) of 31.43 gram of 900 equivalent (EW), 46.4 grams of ethanol, 10.3 grams of water, and stir contained thing approximately 15 minutes.Described ionomer solution is added in catalyst, carbon fiber and the abrasive media in described first bottle.Described first bottle is placed on to upper 72 hour of ball mill with 145 RPM rotations.By adding the ionomer (water of the solid of 28wt.%, the ethanol of 42wt.%, 30wt.%) of 57.1 gram of 900 equivalent (EW) and the solid film solution that 10.7 grams of water has been prepared 16wt.%.
By 11.88 grams of spherical zircite abrasive medias containing the graphitization Vulcan catalyst (being provided by Tanaka Kikinzoku International) of 20% Pt and 1200 grams 5 millimeters being added in the polyethylene bottle of first 500ml, prepare described anode ink.In the polyethylene bottle of second 500ml, add the solution of the ionomer (water of the solid of 28wt.%, the ethanol of 42wt.%, 30wt.%) of 56.64 gram of 900 equivalent (EW), 47.0 grams of ethanol, 30.3 grams of water, 1.7 grams of oleyl amines that comprise 26.7wt.%, the normal propyl alcohol of 55wt.% and water of 18.3wt.%, and stir contained thing approximately 15 minutes.Described ionomer solution is added in the catalyst and abrasive media in described first bottle.First bottle that the solution of described mixing is housed is placed on to upper 48 hour of ball mill with 145 RPM rotations.
At Figure 15 and 16, the negative electrode and the anode composite structure that generate have been shown.Figure 15 has described the scanning electron micrograph of described dry negative electrode composite construction, and described dry negative electrode composite construction has the cathode layer (1510) being formed on non-porous base material (1505) and is formed on the rete (1515) on cathode layer (1510).Figure 16 has described the scanning electron micrograph of described dry anode composite structure, and it has shown that described dry anode composite structure has base material (1605), is formed on the anode layer (1625) on described non-porous base material (1605) and is formed on the nonporous membrane (1615) on described anode layer (1625).
embodiment 5
Negative electrode ink and anode ink as described, have been prepared in embodiments of the invention 1.
By 104.7 grams of ionomer dispersion (DuPont Nafion D2020, the normal propyl alcohol of the solid of 21.4wt.%, the water of 33.1wt.% and 45.5wt.%), the cerous carbonate (III) of 105.5mg, 44.1 grams of normal propyl alcohols and 11.2 grams of water are added in the polyethylene bottle of 250ml.Make described solution mix a whole night.
Four membrane electrode assemblies have been formed as follows.At a slice GDM(, by Freudenberg FCCT KG, provided) surface on, under laminar flow, nonporous membrane solution and negative electrode ink are coated on described GDM base material simultaneously, described non-porous rete is coated in described negative electrode ink layer to form wet composite construction simultaneously.Apply described two-layer after and occurring any be dried in a large number before, by a slice ePTFE(Donaldson D1326) be placed on described wet film surface.After applying described ePTFE, make described wet composite construction standing 10-30 second so that described ePTFE is sucked in described coating solution completely.Then, under the infrared lamp of source temperature with 450 ℉, dry described wet composite construction has base material to form in approximately 10 minutes, is formed on the negative electrode on described base material and is formed on the dry negative electrode composite construction of the nonporous membrane on described negative electrode.In inert nitrogen atmosphere, in 180 ℃, described dry negative electrode composite construction is annealed 15 minutes.
At a slice GDM(, by Freudenburg FCCT KG, provided) surface on, under laminar flow, nonporous membrane solution (four assemblies are used described the first nonporous membrane solution and four assemblies to use described the second nonporous membrane solution) and anode ink are coated on described GDM base material simultaneously, described non-porous rete is coated on described anode ink water layer to form wet composite construction simultaneously.Then, described wet composite construction is placed on and within the infrared lamp of the source temperature with 450 ℉ approximately 10 minutes, to form, there is base material, be formed on the anode on described base material and be formed on the dry anode composite structure of the nonporous membrane on described anode.In inert nitrogen atmosphere, in 180 ℃, described dry negative electrode composite construction is annealed 15 minutes.
Described negative electrode composite construction and described anode composite structure by together with hot pressing to form four MEA.Described four membrane electrode assemblies are assembled in fuel cell pack to form combined electrode component (UEA).
According to the polarization curve scheme of US Council for Automotive Research department of Commerce LLC ' s accelerated test and PEM fuel cell, the scheme (U.S. Council for Automotive Research LLC ' s Accelerated Testing and Polarization Curve Protocols for PEM Fuel Cells, Protocol for Determining Cell/Stack Durability) that is used for measuring battery/heap durability, pile durability test.The hydrogen thoroughly testing procedure of (hydrogen crossover) is the Electrochemical Detection through described film based on molecular hydrogen.For this reason, at anode-side use hydrogen and at cathode side air purge UEA.Use described scheme, by keeping current density to be stabilized in 0.4A/cm 2, make hydrogen flow to anode, make air flow to negative electrode, 134 kPa(absolute pressures with 4.0 stoichiometry with 1.5 stoichiometry) outlet pressure and the operating temperature of 70 ℃ continue 15 minutes, make UEA reach poised state.After the balance of 15 minutes, make current density drop to 0A/cm 2(OCV – open-circuit cell voltage) and the body keeping 3 minutes of still ventilating.After these 3 minutes, be closed to the air of described cathode side and record cell voltage as the function of time.Described cell voltage reduces the index of its degraded that is film using the function as hydrogen infiltration.Particularly, from data, obtain the long durability that described battery drops to the time that 100 mV spend and is used for each battery of comparison and other batteries and observes film.Lower than the values of 20 seconds, be conventionally considered to the limit of rupture.As shown in following table 1, for each UEA, measured the running time that drops to 100 mV after the operation of a few hours.After surpassing the operation of 2000 hours, described four UEA almost do not have (being less than approximately 20%) to drop in time 100 mV, show that described UEA is durable to surpass 2100 hours.
Table 1
Described in detail the present invention and passed through with reference to its specific embodiment, obviously in the situation that the scope modification of the present invention and the variant that define in not departing from additional claims are possible.More specifically, although aspects more of the present invention have been confirmed to be preferably or particularly advantageous herein, the present invention is not intended to necessarily be confined to these preferred aspects of the present invention.

Claims (10)

1. a plurality of fuel cell component coatings are applied to the method on base material simultaneously, described method comprises:
Base material is provided; With
Under laminar flow, two or more solution are coated on described base material simultaneously, non-porous layer solution is coated on the first porous layer solution simultaneously;
Wherein said the first porous layer solution comprises electrode ink and described non-porous layer solution comprises coating solution.
2. method according to claim 1, wherein said method further comprises porous enhancement layer is applied on described non-porous layer solution.
3. method according to claim 2, wherein said method further comprises that dry described the first porous layer solution, described non-porous layer solution and described porous enhancement layer are to be formed on the first porous layer on described base material, non-porous layer on described the first porous layer and the described porous enhancement layer on described non-porous layer.
4. method according to claim 1 is wherein used slit die coating process, swash plate coating process, curtain coating technique or print roll coating technique or its combination to apply described two or more solution simultaneously.
5. method according to claim 1, wherein said laminar flow has the Reynolds number that is less than approximately 50.
6. a plurality of fuel cell component coatings are applied to the method on base material simultaneously, described method comprises:
Base material is provided; With
Under laminar flow, three kinds or more kinds of solution are coated on described base material simultaneously, non-porous layer solution is coated on the first porous layer solution simultaneously;
Wherein said the first porous layer solution comprises electrode ink and described non-porous layer solution comprises coating solution.
7. method according to claim 6, is wherein coated in described the first porous layer solution on microporous layers solution simultaneously, and described microporous layers is coated on described base material simultaneously.
8. method according to claim 7, wherein said method further comprises that dry described microporous layers solution, described the first porous layer solution and described non-porous layer solution are to form microporous layers, the first porous layer and non-porous layer.
9. method according to claim 6, wherein said base material is gas diffusion media.
10. manufacture a method for membrane electrode assembly, described method comprises:
Two or more solution are coated on the first base material to form cathode substrate simultaneously, wherein under laminar flow, carry out described coating, coating solution is coated in cathode solution simultaneously;
Two or more solution are coated on the second base material to form anode base material simultaneously, wherein under laminar flow, carry out described coating, coating solution is coated on anodic dissolution simultaneously; With
Described cathode substrate is hot-pressed onto to described anode base material, makes negative electrode and the relative both sides of anode at described film.
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